The First Ternary Phase in the Ga–Sn–Pd System: Synthesis, Crystal Structure, and Catalytic Properties of Ga2+x+ySn4–xPd9. Issue 29 (8th August 2017)

• Record Type: Journal Article
• Authors: Matselko, Oksana; Burkhardt, Ulrich; Prots, Yurii; Zimmermann, René R.; Armbrüster, Marc; Gladyshevskii, Roman; Grin, Yuri
• Is Part Of: European journal of inorganic chemistry. Issue 29(2017)
• Page Start: 3542
• Page End: 3550
• Publication Date: 2017-08-08
• Subjects: Intermetallic phases -- Electronic structure -- Palladium -- Hydrogenation; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700481
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The new ternary compound Ga2+ x + y Sn4– x Pd9 ( x = 0.72, y = 0.06) was synthesized by arc melting of the elements. The crystal structure was solved from the single‐crystal X‐ray diffraction data [space group Fd 3 m, a = 12.4048(9) Å, Z = 8, 222 reflections, R F = 0.035]. The crystal structure of Ga2+ x + y Sn4– x Pd9 is related to the Ti2 Ni type and its filled derivatives ( η ‐phases) with additional Pd atoms at octahedrally and tetrahedrally coordinated sites. The electronic density of states of Ga2+ x + y Sn4– x Pd9 is similar to those of the binary compounds GaPd and GaPd2, which are catalytically active in the semihydrogenation of acetylene. Quantum‐chemical calculations revealed a distribution of the electron localizability indicator analogous to that for GaPd in a system of heteroatomic electron‐deficient two‐center interactions. In contrast to the arrangement in GaPd, the spatial organization of these interactions hinders the formation of isolated active sites on the surface and results in a relatively low catalytic activity for Ga2+ x + y Sn4– x Pd9 . Abstract : The crystal structure of Ga2+ x + y Sn4– x Pd9 is related to the Ti2 Ni type, whereas its electronic structure is similar to those of the binary compounds GaPd and GaPd2, which are catalytically active in acetylene semihydrogenation. However, the isotropic organization of electron‐deficient two‐center Pd–Ga and Pd–Sn interactions in the position space may prevent the formation of isolated active Pd sites.